US4384096A - Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems - Google Patents
Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems Download PDFInfo
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- US4384096A US4384096A US06/219,480 US21948080A US4384096A US 4384096 A US4384096 A US 4384096A US 21948080 A US21948080 A US 21948080A US 4384096 A US4384096 A US 4384096A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- Polymeric water-soluble thickening agents are widely known and used in many aqueous systems including latex paints and other aqueous coating compositions.
- New aqueous emulsion polymers have been discovered which provide stable liquid emulsions having low viscosity and relatively high solids content under acidic conditions, but which become very efficient polymeric thickeners for many aqueous systems when treated with base.
- These new products are preferably prepared in the form of an aqueous colloidal dispersion of water-insoluble polymer by emulsion polymerization at a pH of about 2.5 to 5.0 of three essential ethylenically unsaturated monomeric components: (A) a carboxylic acid monomer, (B) a nonionic vinyl monomer and (C) a nonionic vinyl surfactant ester.
- a polymer useful as a pH responsive thickener for aqueous systems comprising an aqueous emulsion copolymer of:
- R is --COOX and R' is H or --CH 2 COOX;
- R is CH 3 and R' is H
- X is H or C 1 -C 4 alkyl
- Y is H and Z is --COOR, --C 6 H 4 R', CN, Cl, ##STR2## or --CH ⁇ CH 2 ;
- Y is CH 3 and Z is --COOR, --C 6 H 4 R', CN or --CH ⁇ CH 2 ; or
- R is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl
- R' is H, Cl, Br, or C 1 -C 4 alkyl
- R" is C 1 -C 8 alkyl
- R" is C 8 -C 20 alkyl or C 8 -C 16 alkylphenyl
- n is an average number from about 6-100 and m is an average number from about 0-50 provided that n ⁇ m and ⁇ (n+m) is about 6-100; said polymer being stable as an aqueous colloidal dispersion at a pH lower than about 5.0 but becoming an effective thickener for aqueous systems upon adjustment to a pH of about 5.5-10.5 or higher.
- the emulsion polymerization is normally carried out under acidic conditions in which the carboxylic acid groups are in protonated form to insolubilize the polymer and give a liquid emulsion.
- the polymeric thickener is added as such a liquid colloidal dispersion, the finely divided polymer particles dissolve almost instantly upon pH adjustment.
- the ease of handling, metering, and dispersing the liquid emulsion polymer, the rapid solubilization by controlled pH adjustment, and the highly desirable rheological properties make this liquid emulsion polymer a most effective and efficient thickening agent for a wide variety of applications including latex paints and other aqueous coating compositions.
- novel liquid emulsion polymers of this invention require three essential components: (A) about 15-60 weight percent of a C 3 -C 8 ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer, (B) about 15-80 weight percent of a copolymerizable nonionic vinyl monomer, and (C) about 1-30 weight percent of certain nonionic vinyl surfactant esters. It has been discovered that the effectiveness of these liquid emulsion polymers as a pH responsive thickener for many aqueous products is critically dependent on these components.
- the acid component A provides the requisite pH responsiveness; the nonionic vinyl comonomer B provides an extended polymer backbone and added hydrophiliclipophilic balance; and the nonionic vinyl surfactant ester C provides an in situ, bound surfactant to control the rheology of the aqueous system containing the solubilized polymeric thickener.
- the proportions of the individual monomers can be varied to achieve optimum properties for specific applications.
- the liquid emulsion polymer requires about 15-60 weight percent based on total monomers of a C 3 -C 8 ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer of the formula: ##STR4## where R is H and R' is H, C 1 -C 4 alkyl, or --CH 2 COOX; R is --COOX and R' is H or --CH 2 COOX; or R is CH 3 and R' is H; and X is H or C 1 -C 4 alkyl.
- Acrylic or methacrylic acid or a mixture thereof with itaconic or fumaric acid are preferred, but crotonic and aconitic acid and half esters of these and other polycarboxylic acids such as maleic acid with C 1 -C 4 alkanols are also suitable, particularly if used in minor amount in combination with acrylic or methacrylic acid.
- polycarboxylic acid monomers and half esters can be substituted for a portion of the acrylic or methacrylic acid, e.g., about 1-15 weight percent based on total monomers.
- Y is H and Z is --COOR, --C 6 H 4 R', CN, Cl, ##STR5## or --CH ⁇ CH 2 ;
- Y is CH 3 and Z is --COOR, --C 6 H 4 R', CN or --CH ⁇ CH 2 ; or
- R is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl
- R' is H, Cl, Br, or C 1 -C 4 alkyl
- R" is C 1 -C 8 alkyl.
- Typical of such monomers are the C 1 -C 8 alkyl and C 2 -C 8 hydroxyalkyl esters of acrylic and methacrylic acid including ethyl acrylate, ethyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate; styrene, vinyltoluene, t-butylstyrene, isopropylstyrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate; acrylonitrile, methacrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride, and the like.
- a monovinyl ester such as ethyl acrylate or a mixture thereof with styrene, hydroxyethy
- the third required monomer component is about 1-30 weight percent based on total monomers of a nonionic vinyl surfactant ester of the formula: ##STR6## where R is H or CH 3 ; each R' is C 1 -C 2 alkyl; R" is C 8 -C 20 alkyl or C 8 -C 16 alkylphenyl; n is an average number from about 6-100 and m is an average number from about 0-50 provided that n ⁇ m and ⁇ (n+m) is about 6-100.
- acrylate and methacrylate surfactant esters selected from the group consisting of:
- alkylphenoxypoly(ethyleneoxy)ethyl acrylates of the formula: ##STR7## where R is H or CH 3 ; Y' is C 8 -C 16 alkyl, and n is about 6-100;
- alkoxypoly(ethyleneoxy)ethyl acrylates of the formula: ##STR8## where R is H or CH 3 , R" is C 8 -C 20 alkyl, and n is about 6-50; and
- alkoxypoly(alkyleneoxy)ethyl acrylates of the formula: ##STR9## where R is H or CH 3 , each R' is C 1 -C 2 alkyl, R" is C 8 -C 20 alkyl, and n is about 6-50 and m is about 1-40.
- These essential vinyl surfactant esters are the acrylic or methacrylic acid esters of certain nonionic surfactant alcohols.
- Such surfactant esters are known in the art.
- Junas et al. U.S. Pat. No. 3,652,497 describe the use of alkylphenoxyethyleneoxyethyl acrylates in preparing several other polymeric surfactant thickeners.
- 4,075,411 describes several processes for preparing such vinyl surfactant esters including the acid catalyzed condensation of commercially available nonionic polyoxyalkylene surfactant alcohols such as alkylphenoxypoly(ethyleneoxy)ethyl alcohol and block-polymeric glycols with acrylic, methacrylic, crotonic, maleic, fumaric, itaconic or aconitic acid. Alternate esterification methods including alcoholysis and transesterification are also described.
- Other suitable vinyl surfactant esters can be prepared from monoethers of mixed or heteric ethyleneoxypropyleneoxy-butyleneoxy polyglycols such as described in Patton U.S. Pat. No. 2,786,080. Additional surfactant alcohols which can be esterified for use herein are given in "McCutcheon's Detergents and Emulsifiers" 1973, North American Edition, Allured Publishing Corp., Ridgewood, N.J. 07450.
- vinyl surfactant esters i.e., those defined by Formula III and particularly the alkylphenoxy and alkoxyethyl esters of Formulas IV-VI, are useful in preparing the novel emulsion polymers described herein. It is essential that the surfactant be incorporated in the liquid emulsion product by copolymerization.
- the requisite surfactant esters are prepared by the direct acid catalyzed esterification of the appropriate surfactant alcohol with an excess of the carboxylic acid monomer used as Component A. The resulting mixture with excess acid can be used directly in the copolymerization provided that at least 30 percent, and preferably 50-70 percent or more, of the surfactant alcohol in the mixture is esterified.
- the vinyl surfactant ester can also be recovered, purified by conventional means using an appropriate inhibitor such as hydroquinone or p-tert-butylcatechol to prevent undesired homopolymerization, and then used to prepare the liquid emulsion polymers.
- an appropriate inhibitor such as hydroquinone or p-tert-butylcatechol to prevent undesired homopolymerization, and then used to prepare the liquid emulsion polymers.
- hydrophiliclipophilic balance (HLB) of the vinyl surfactant ester is an important factor in the performance of the resulting emulsion polymer.
- HLB hydrophiliclipophilic balance
- increasing the chain length of the terminal hydrophobic alkoxy or alkylphenoxy group will increase the efficiency of the resulting polymer as a thickener.
- decreasing the number of polyethyleneoxy groups increases thickener efficiency.
- the hydrophilic balance of the copolymer product can be adjusted to a degree by the judicious selection of the nonionic vinyl monomer B; e.g., a soft, (lower alkyl)poly(ethyleneoxy)ethyl ester of Formula VI can be used in a system with mixture of ethyl acrylate and a hard comonomer such as styrene.
- a soft, (lower alkyl)poly(ethyleneoxy)ethyl ester of Formula VI can be used in a system with mixture of ethyl acrylate and a hard comonomer such as styrene.
- it is critical to the performance of these products that they contain an effective amount of an in situ, bound surfactant to control the rheology of the aqueous system thickened with the solubilized emulsion polymer.
- novel liquid emulsion copolymers are conveniently prepared from the above-described monomers by conventional emulsion polymerization at an acid pH lower than about 5.0 using free-radical producing initiators, usually in an amount from 0.01 percent to 3 percent based on the weight of the monomers.
- the free-radical producing initiators conveniently are peroxygen compounds especially inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, sodium persulfate; peroxides such as hydrogen peroxide; organic hydroperoxides, for example, cumene hydroperoxide, t-butyl hydroperoxide; organic peroxides, for example, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peracetic acid, and perbenzoic acid (sometimes activated by a water-soluble reducing agent such as ferrous compound or sodium bisulfite); as well as other free-radical producing materials such as 2,2'-azobisisobutyronitrile.
- inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, sodium persulfate
- peroxides such as hydrogen peroxide
- organic hydroperoxides for example, cumene hydroperoxide, t-
- a chain transfer agent and an additional emulsifier can be used.
- Representative chain transfer agents are carbon tetrachloride, bromoform, bromotrichloromethane, long chain alkyl mercaptans and thioesters such as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, butyl thioglycolate, isooctyl thioglycolate, and dodecyl thioglycolate.
- the chain transfer agents are used in amounts up to about 10 parts per 100 parts of polymerizable monomers.
- anionic emulsifier is included in the polymerization charge and one or more of the known nonionic emulsifiers may also be present.
- anionic emulsifiers are the alkali metal alkyl aryl sulfonates, the alkali metal alkyl sulfates and the sulfonated alkyl esters.
- emulsifiers sodium dodecylbenzenesulfonate, sodium disecondary-butylnaphthalene sulfonate, sodium lauryl sulfate, disodium dodecyldiphenyl ether disulfonate, disodium n-octadecylsulfosuccinamate and sodium dioctylsulfosuccinate.
- ingredients well known in the emulsion polymerization art may be included such as chelating agents, buffering agents, inorganic salts and pH adjusting agents.
- Polymerization at an acid pH lower than about 5.0 permits direct preparation of an aqueous colloidal dispersion with relatively high solids content without problems of undue viscosity.
- the copolymerization is carried out at a temperature between about 60° C. and 90° C. but higher or lower temperatures may be used.
- the polymerization is carried out batchwise, stepwise or continuously with batch and/or continuous addition of the monomers in a conventional manner.
- the essential monomers can be copolymerized in such proportions, and the resulting emulsion polymers can be physically blended, to give products with the desired balance of properties for specific applications. For example, if a more viscous product is desired, the acid and surfactant monomer content can be increased. Greater flexibility and coalescence can be obtained with higher amounts of ethyl acrylate. Addition of styrene as a second nonionic vinyl monomer will increase to a higher pH the adjustment required to dissolve the emulsion in an aqueous coating composition.
- liquid emulsion polymer thickeners are obtained by copolymerization of about 40-50 weight percent of methacrylic acid, about 35-50 weight percent of ethyl acrylate, and about 2-12 weight percent of the methacrylic ester of a C 9 -alkylphenoxy(ethyleneoxy) 9 ethyl alcohol.
- copolymer products prepared by emulsion polymerization at an acid pH are in the form of stable aqueous colloidal dispersions usually with a typical milky latex appearance.
- a liquid emulsion contains the copolymer dispersed as discrete particles having average particle diameters of about 500-3000 A, preferably about 1000-1750 A, as measured by light refraction. Dispersions containing polymer particles smaller than about 500 A are difficult to stabilize while particles larger than about 3000 A reduce the ease of dispersion in the aqueous products to be thickened.
- emulsion copolymers will normally have number average molecular weights of at least about 30,000 as determined by gel permeation chromatography. To provide most effective thickening with copolymers which are water-soluble when neutralized, molecular weights within the range of about 200,000 to 5,000,000 are preferred. In terms of a standard Brookfield viscosity measured as a 1 percent aqueous solution in ammonium salt form at pH 9 and 25° C., a copolymer with a viscosity of about 50-50,000 cps, and preferably about 100-30,000 cps, is particularly desirable for many applications.
- aqueous colloidal dispersion at an acid pH of about 2.5-5.0 the copolymer is particularly useful.
- aqueous dispersion may contain about 10-50 weight percent of polymer solids yet be of relatively low viscosity. Thus it is readily metered and blended with aqueous product systems.
- the dispersion is pH responsive.
- a base such as ammonia, an amine or a non-volatile inorganic base such as sodium hydroxide, potassium carbonate or the like
- the aqueous mixture becomes translucent or transparent as the polymer dissolves at least partially in the aqueous phase with a concurrent increase in viscosity.
- This neutralization can occur in situ when the liquid emulsion polymer is blended with an aqueous solution containing a suitable base. Or if desired for a given application, pH adjustment by partial or complete neutralization can be carried out before or after blending the liquid emulsion polymer with an aqueous product.
- liquid emulsion polymer as applied to the new thickener of this specification means that the thickener is an emulsion polymer because the polymer was prepared by emulsion polymerization even though the polymer per se may be (and generally is) a solid at room temperature but is a "liquid” emulsion polymer because it is in the form of a liquid solution or dispersion.
- pH viscosity response curves for several typical liquid emulsion polymers prepared by copolymerizing methacrylic acid (MAA), ethyl acrylate (EA), and nonylphenoxypoly(ethyleneoxy) 9 ethyl methacrylate (VSE-1A) are shown in the FIGURE as determined in aqueous media at a concentration of 1 percent by weight and at room temperature. Note that the pH range of initial viscosity build can be controlled by variation in the composition of the emulsion copolymer.
- emulsion polymers are useful as water-soluble thickeners for a wide variety of applications ranging from cosmetics to drilling muds, but particularly for aqueous coating compositions.
- liquid emulsion polymers described herein are particularly useful as thickeners for a wide variety of water-based compositions including aqueous brine and polymer solutions as well as aqueous slurries and colloidal dispersions of water-insoluble inorganic and organic material including compositions such as natural rubber, synthetic or artificial latexes and aqueous products containing such materials.
- Synthetic latexes which may be thickened with the liquid emulsion polymers are aqueous colloidal dispersions of water-insoluble polymers prepared by emulsion polymerization of one or more ethylenically unsaturated monomers.
- Typical of such synthetic latexes are emulsion copolymers of monoethylenically unsaturated compounds such as styrene, methyl methacrylate, acrylonitrile with a conjugated diolefin such as butadiene or isoprene; copolymers of styrene, acrylic and methacrylic esters, copolymers of vinyl halide, vinylidene halide, vinyl acetate and the like.
- ethylenically unsaturated monomers or mixtures thereof can be emulsion polymerized to form synthetic latexes.
- Representative monomers are vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, t-butylstyrene, chlorostyrene, vinyltoluene; conjugated dienes such as butadiene, isoprene, and 2-chloro-1,3-butadiene; vinyl chloride, vinylidene chloride, acrylonitrile, and methacrylonitrile; acrylic and ⁇ -hydroxyalkyl acrylic esters; vinyl acetate, vinyl propionate, ethylene and methyl isopropenyl ketone.
- unsaturated carboxylic acid monomers such as defined by Formula I are frequently used in preparing the base polymer for latex paints.
- the artificial latexes are latexes which are produced by the dispersion or redispersion of pre-formed water-insoluble polymers or solutions thereof.
- the artificial latexes are produced by known emulsification processes, e.g., by addition of water with stirring until phase inversion occurs, by high shear mixing with water at elevated temperatures or by dilution of a mixture of water and a water-miscible solvent followed by stripping to remove the solvent.
- a surfactant is required in the emulsification process unless hydrophilic groups are attached to the polymer in sufficient quantity to assist dispersion but in insufficient quantity to produce water-solubility.
- Such artificial latexes are produced from polymers which are not prepared readily from monomers by emulsion polymerization, either because no substantial polymerization at a commercially acceptable rate is obtained under usual emulsion polymerization conditions, such as with isobutene, or because a particular form of the polymerized monomer is desired, for example, stereospecific polyisoprene, stereospecific polybutadiene and the like.
- Representative pre-formed polymers are polymers and copolymers of the mono-olefins having from 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, hexene, octene, dodecene, hexadecene, octadecene and especially those mono-olefins having up to 8 carbon atoms.
- Especially common types are the various ethylene/propylene copolymers.
- alkyd resins block and graft copolymers
- styrene/butadiene graft and block copolymers e.g., epoxy resins such as the reaction products of epichlorohydrin and bisphenol-A; and thermosettable vinyl ester resins; e.g., the reaction products of approximately equivalent amounts of a polyepoxide and an unsaturated monocarboxylic acid such as acrylic acid and methacrylic acid or unsaturated fatty acids such as oleic acid.
- the thickeners of this invention are advantageous for use with the water-based compositions according to the foregoing description and with compositions containing those materials, especially coating compositions of various types. Mixtures of two or more thickeners may be used, if desired.
- the latex polymers used in coating compositions are preferably film-forming at temperatures below about 25° C., either inherently or through the use of plasticizers.
- Such coating compositions include water-based consumer and industrial paints; sizing, adhesives and other coatings for paper, paperboard, textiles; and the like.
- these latex coating compositions contain added pigments, fillers and extenders such as titanium dioxide, barium sulfate, calcium carbonate, clays, mica, talc, silica and the like.
- the novel liquid emulsion polymers described herein are compatible with most latex paint systems and provide highly effective and efficient thickening. Suitable results are obtained using about 0.05-5.0 weight percent of the liquid emulsion polymer based on total weight of solids, and preferably about 0.1-2.0 weight percent.
- aqueous compositions thickened with the liquid emulsion polymers of this invention preferably are those in which any dispersing or solvating liquid present consists of greater than 50 percent by weight of water.
- VSE vinyl surfactant ester
- Nonylphenoxypoly(ethyleneoxy) 9 ethyl Methacrylate A stainless steel reactor was charged with 474 parts (0.68 mole) of nonylphenoxypoly(ethyleneoxy) 9 ethanol (Igepal® CO-660 from GAF), 0.31 part of hydroquinone and 0.16 part of Ionol® (2,6-di-t-butyl-p-cresol from Shell Chemical Co.). Then 8.6 parts of 90 ⁇ 2 percent H 2 SO 4 was added with stirring followed by 526 parts (6.1 moles) of methacrylic acid stabilized with monomethyl ether of hydroquinone (MEHQ). With a slow stream of air bubbling through the reactant mixture, the reactor was heated at 105° C.
- MEHQ monomethyl ether of hydroquinone
- liquid product VSE-1A recovered.
- VSE-1A liquid product recovered.
- the neat product contained 47.2 weight percent surfactant ester (90 percent conversion), 4.8 weight percent unreacted surfactant, 46.8 weight percent excess methacrylic acid and 1.2 weight percent water, sulfuric acid and stabilizers.
- the vinyl surfactant ester can be used neat for the preparation of the desired emulsion copolymers or the ester can be recovered by conventional means.
- a conversion to vinyl ester of at least 30-40 percent is desirable to avoid too high free surfactant level in the subsequent emulsion polymerization.
- 70-90 percent conversion can normally be obtained at 100°-120° C. in 2-4 hours.
- Example 1A The direct sulfuric acid catalyzed esterification process of Example 1A was used to prepare the above ester from the monomethyl ether of propylene glycol (Dowanol® PM from The Dow Chemical Company) condensed with four moles of butylene oxide and then 20 moles of ethylene oxide using an alkaline catalyst.
- the neat vinyl surfactant ester (VSE-1F) can be used without further purification in the preparation of the liquid emulsion copolymer.
- the polymerization is carried out in a stainless steel, jacketed reactor equipped with stirrer and feed pumps using the concurrent addition technology of Miller et al. U.S. Pat. No. 3,563,946 in which separate monomer mix and aqueous feed solutions are added concurrently to an initial aqueous reactor charge stirred at 90 rpm and preheated to a desired temperature.
- the addition of monomer and aqueous initiator is completed, normally in about 2-4 hours, the emulsion is stirred an additional 1.5 hours to finish the polymerization. Then the reactor is cooled and the liquid emulsion polymer filtered through 100 and 200 mesh screens.
- the resulting liquid emulsion polymer contained 20.1 weight percent solids at pH 3.5 and had a 1 percent aqueous solution viscosity in ammonium salt form at pH 9 of 400 cps (Brookfield Model LVT, #2 spindle, 12 rpm, 25° C.).
- liquid emulsion polymer was prepared in which 6 parts of itaconic acid was substituted for 6 parts of methacrylic acid.
- the resulting liquid product contained 19.9 weight percent solids at pH 3.5 and had a 1 percent aqueous solution Brookfield viscosity of 1090 cps in ammonium salt form.
- liquid emulsion polymers differ from LEP-2C-1 in the proportion of components.
- the compositions are shown in Table I.
- liquid emulsion polymers differ from LEP-2D-1 in the proportion of components.
- the compositions are shown in Table I.
- a stirred glass reactor was charged with 271 parts of water, 2.0 parts of Conco Sulfate 219 (sodium salt of ethoxylated, sulfated lauryl alcohol from Continental Chemical Co.) and 0.1 part of Versenex® 80 (40 percent). The reactor charge was purged with nitrogen while stirring and was heated to 69° C.
- Conco Sulfate 219 sodium salt of ethoxylated, sulfated lauryl alcohol from Continental Chemical Co.
- Versenex® 80 40 percent
- a monomer mixture of 24.7 parts of methacrylic acid, 31.6 parts of ethyl acrylate, 19.0 parts of the product solution of Example 1-C containing 40.5 percent of vinyl surfactant ester-1D and 59.5 percent of methacrylic acid and 2.0 parts Conco Sulfate 219 was prepared in a dropping funnel.
- This liquid emulsion polymer differs from LEP-2G-1 in the proportion of components.
- the A ingredients are ground together at high speed for 20 minutes using a Cowles grinder. Then at reduced speed premixed ethylene glycol and glycol ether are added followed by the Everflex E® latex.
- the liquid emulsion polymer thickener (20 percent solids) and appropriate amount of water can be added immediately or later as desired for test purposes.
- the A ingredients are ground together at high speed for 20 minutes using a Cowles grinder. Then at reduced speed the B ingredients including premixed propylene glycol and phenoxyethanol are added.
- the emulsion polymer thickener (20 percent solids) and the balance of the water can be added immediately or later as desired for test purposes.
- liquid emulsion polymers can be incorporated in latex paints in several ways:
- Leneta Leveling Test (The Leneta Co., Ho-Ho-Kus, NJ 07423). A paint sample is drawn down using a Leneta leveling test blade and the dried paint film compared visually with eleven Leneta levelness standards numbered 0-10 with 10 being perfect leveling.
- Leneta Anti-Sag Test-- (The Leneta Co., Ho-Ho-Kus, NJ 07423).
- a presheared sample of paint is drawn down with the Leneta anti-sag meter on Leneta drawdown chart form 7B positioned horizontally on a flat glass or metal plate.
- the chart is then immediately placed in a vertical position with the paint stripes horizontal and left edge (thinnest stripe) at the top, and allowed to dry.
- Each stripe, ranging in wet film thickness from 3 to 12 mils, is considered as having the same rating number as the notch by which it has been applied.
- index stripe The highest number (thickest) stripe that does not touch the one below itself is referred to as the index stripe, and its number is the Anti-Sag index of the paint.
- the practical interpretation of ratings is empirical and strongly subjective. Optimum sag resistance depends on the type of coating, but in general, an index of 8 through 12 is considered good to excellent.
- Color Acceptance--A test paint is prepared by mixing 0.5 g of color tint with 24.5 g of formulated paint and drawn down on a primed-unprimed chart (Leneta 1B) using a 7 mil gap clearance blade. A 2-3 cm diameter circular area overlapping the primed-unprimed chart surface is rubbed with a finger until decided resistance is felt. The film is dried and rated as: (1) acceptable-no visual difference in rubbed area; (2) pigment flocculation-rubbed area lighter in color or (3) colorant flocculation-rubbed area darker in color.
- Gloss--ASTM Method D-523-67 is used to measure the Gardner 60° gloss of paint test panels. A gloss rating of 30-65 generally desirable for interior semigloss latex paints.
- Table I presents typical test results for an interior flat latex paint and an interior semigloss latex paint prepared as described for Formulations 3A and 3B using the representative liquid emulsion polymers described in Example 2.
- Test results such as shown in Table I demonstrate the utility of the water-based liquid emulsion polymers described herein as a pH responsive thickener for aqueous compositions.
- the liquid emulsion polymers can be tailored to give optimum thickening for many applications including particularly those containing natural, synthetic and artificial latexes.
- Table II presents typical test results comparing two liquid emulsion polymer thickeners with three commercial cellulose ether thickeners commonly used in latex paints.
- the effective thickening observed even with a lower viscosity LEP product suggests association of the LEP thickener with other components of the paint formulation as well as hydration by water.
- Table III presents typical data for the liquid emulsion polymer described in Example 2A (48.0 MAA/42.0 EA/10.0 VSE-1A; 20.1 percent solids, 1 percent viscosity of 305 cps at pH 9.0) used as a thickener in two paint formulations.
- Table III presents typical data for the liquid emulsion polymer described in Example 2A (48.0 MAA/42.0 EA/10.0 VSE-1A; 20.1 percent solids, 1 percent viscosity of 305 cps at pH 9.0) used as a thickener in two paint formulations.
- Similar data for a commercial cellulose ether thickener is also given. Note that the liquid emulsion polymer is more efficient as a thickener, provides improved flow and leveling with markedly reduced spattering and yet retains many of the desirable properties of the cellulose ether thickener.
- liquid emulsion polymers as thickeners for aqueous compositions including inorganic solutions and slurries.
- LEP-2A as a thickener for several unformulated vinyl-acrylic paint latexes was determined using several commercial latexes blended with a 2 percent aqueous solution of LEP-2A neutralized to pH 9 with NH 4 OH. The blended aqueous compositions were adjusted to 21 percent total solids and Brookfield viscosities were determined with results shown in Table V.
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Abstract
Description
CH.sub.2 ═CYZ (II)
CH.sub.2 ═CYZ (II)
______________________________________ (1) Initial Reactor Charge* 374.0 parts Condensate water 0.0075 part Versenex® 80 chelant (40% solids) 2.0 parts Gafac® RE-610 anionic surfactant (2) Monomer Mix - Feed Rate - 4 hours 48.0 parts Methacrylic acid (MAA) 42.0 parts Ethyl acrylate (EA) 10.0 parts Vinyl surfactant ester (VSE-1A) 6.0 parts Igepal® CO-530 nonionic surfactant (3) Aqueous Feed Mix - Feed Rate - 4 hours 69.8 parts Condensate water 0.0025 part Versenex® 80 chelant (40%) 0.4 part Sodium hydroxide 2.0 parts Dowfax® 2A1 anionic surfactant (45% solids) 1.0 part Gafac® RE-610 0.5 part Sodium persulfate ______________________________________ *Notes: Quantities are in parts by weight based on 100 parts total monomer Versenex® 80 sodium diethylenetriaminepentaacetic acid, 40% active solids from The Dow Chemical Company Gafac® RE610 a nonylphenoxypoly(ethyleneoxy)phosphate ester in free acid form from GAF VSE1A neat vinyl surfactant ester of Example 1A (100% active basis) Igepal® CO530 nonylphenoxypoly(ethyleneoxy).sub.5 ethanol from GAF Dowfax® 2A1 sodium dodecyldiphenyl ether disulfonate from The Dow Chemical Company
______________________________________ Formulation 3A - Interior Flat Latex Paint Ingredients* Lbs Gallons ______________________________________A. Water 300 36.06 Pigment dispersant (25% Tamol® 731) 12 1.31 Defoamer (Drew L-475) 2 0.26 Preservative (Dowicil® 75) 1 0.08 Surfactant (Triton® X-100) 5 0.56 Aluminum silicate (ASP-400) 100 4.66 CaCO.sub.3 (snowflake white) 125 5.54 Titanium dioxide (Ti-Pure® R-931) 250 7.79 B. Ethylene glycol 25 3.00 Glycol ether (Texanol) 10 1.26 Everflex E® latex (55%) 250 27.78 C. LEP Thickener and water** 95.6 11.47 1175.6 99.77 ______________________________________ *Notes: Tamol® 731 sodium salt of maleic anhydride/diisobutylene copolymer from Rohm & Haas Drew L475 liquid defoamer from Drew Chemical Corp., Parsippany, NJ 07054 Dowicil® 75 1(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chlorid to which sodium bicarbonate has been added, from The Dow Chemical Co. Triton® X100 octylphenoxypolyethoxyethanol from Rohm & Haas ASP400 Pigment grade aluminum silicate from Engelhard Minerals & Chem Corp., Iselin, NJ Snowflake White Pigment grade calcium carbonate from Thompson, Weinmann Co., Cartersville, GA 30120 TiPure® R931 TiO.sub.2 pigment from duPont Texanol 2,2,4trimethylpentanediol-1,3 monoisobutyrate from Eastman Chemical Products, Inc., Kingsport, TN 37662 Everflex E® latex vinyl acetateacrylic copolymer latex, sometimes called "vinylacrylic latex" or less commonly "vinylacrylate latex" from W. R. Grace Co. **LEP Thickener normally about 1.0-6.0 lbs (100% solids basis)/100 gal plus water to balance
______________________________________ Formulation 3B - Interior Semigloss Latex Paint Ingredients* Lbs Gallons ______________________________________ A. Water 93 11.18 Pigment dispersant (25% Tamol® 731) 11 1.20 Defoamer (Nopco® NDW) 2 0.27 Propylene glycol 32 3.84 Preservative (Dowicil® 75) 1.3 0.10 Titanium dioxide (Ti-Pure® R-900) 275 7.95 B Defoamer (Nopco® NDW) 4 0.53 Surfactant (Triton® GR7M) 2 0.23 Surfactant (Dowfax® 2A1) 2 0.21 Rhoplex® AC 490 (46.5%) 590 66.67 Propylene glycol 32 3.84 Phenoxyethanol coalescing agent 10 1.09 C. LEP Thickener and water** 74.0 8.87 1128.3 105.98 ______________________________________ *Notes: Tamol® 731 sodium salt of maleic anhydride/diisobutylene copolymer from Rohm & Haas Nopco® NDW nonionic liquid defoamer from Diamond Shamrock Chemical Process Div. Dowicil® 75 1(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chlorid to which sodium bicarbonate has been added, from The Dow Chemical Co. TiPure® R900 TiO.sub.2 pigment from duPont Triton® GR7M dioctyl sodium sulfosuccinate from Rohm & Haas Dowfax® 2A1 sodium dodecyldiphenyl ether disulfonate from The Dow Chemical Co. Rhoplex® AC 490 acrylic emulsion latex from Rohm & Haas **LEP Thickener normally about 1.0-6.0 lbs (100% solids basis)/100 gal plus water to balance
TABLE I __________________________________________________________________________ LIQUID EMULSION POLYMER IN LATEX PAINT Emulsion Polymer Evaluation (3)* Comonomers, Wt % (1)* (2)* Paint LEP Visc LEP (A) R COOH (B) Co-- (C) VSE % Solids 1% Visc Base Wt KU LL LAS __________________________________________________________________________ 2A 48.0 MAA 42.0 EA 10.0 1A 20.1 400 3A 4.5 101 7 12 3B 2.75 85 5 12 2B 42.0 MAA 42.0 EA 10.0 1A 19.9 1090 3A 3.0 86 7 <3 +6.0 IA 3B 2.5 79 5 12 2C-1 48.3 MAA 41.7 EA 10.0 1A 19.8 390 3A 4.5 99 5 12 3B 2.5 82 5 12 2C-2 48.3 MAA 31.7 EA 20.0 1A 19.8 310 3A 4.5 94 6 12 3B 2.5 79 5 12 2C-3 38.3 MAA 51.7 EA 10.0 1A 20.1 870 3A 4.5 96 5 12 3B 2.5 81 5 12 2C-4 38.3 MAA 41.7 EA 20.0 1A 19.8 220 3A 4.5 83 7 10 3B 2.5 78 5 12 2C-5 31.2 MAA 45.0 EA 10.0 1A 21.9 7300 3A 5.0 101 6 12 +13.8 AA 3B 2.75 106 5 12 2D-1 42.0 MAA 37.2 EA 20.8 1B 21.6 1100 3A 5.0 70 -- -- 3B 3.5 119 -- -- 2D-2 42.1 MAA 18.6 EA 20.8 1B 21.8 800 3A 5.0 94 8 9 +18.6 S 3B -- -- -- -- 2D-3 42.0 MAA 37.2 S 20.8 1B 21.5 600 3A 5.0 <60 -- -- 3B 3.5 83 -- -- 2D-4 42.2 MAA 32.6 EA 6.6 1B 19.8 100 3A -- -- -- -- +18.6 VAc 3B 5.0 106 3 12 2D-5 18.7 MAA 55.1 EA 11.5 1B 20.1 18400 3A -- -- -- -- +15.0 HEA (5%) 3B -- -- -- -- 2E 47.8 MAA 42.0 EA 10.2 1C 21.4 9200 3A 3.5 110 5 12 3B 2.0 106 3 12 2F 42.2 MAA 37.2 EA 20.6 1D 21.7 450 3A 5.0 77 -- -- 3B 5.0 98 3 12 2G-1 46.8 MAA 41.4 EA 11.8 1E 20.5 21000 3A 5.0 130 4 12 3B 2.5 128 4 12 2G-2 49.6 MAA 44.1 EA 6.3 1E 19.0 325 3A 5.0 98 9 10 3B 3.0 112 5 12 2H 48.3 MAA 41.7 EA 10.0 1F 20.0 288 3A 4.5 102 3 12 3B 2.5 93 4 12 __________________________________________________________________________ *Notes: (1) Comonomers, wt % based on total monomers (A) MAA methacrylic acid IA itaconic acid AA acrylic acid (B) EA ethyl acrylate S styrene HEA 2hydroxyethyl acrylate VAc vinyl acetate (C) Vinyl surfactant ester from 1A nonylphenoxypoly(ethyleneoxy).sub.9 ethanol 1B nonylphenoxypoly(ethyleneoxy).sub.39 ethanol 1C dodecylphenoxypoly(ethyleneoxy).sub.10 ethanol 1D octyloxypoly(ethyleneoxy).sub.19 ethanol 1E hexadecyloxypoly(ethyleneoxy).sub.39 ethanol 1F methoxypropoxypoly(butyleneoxy).sub.4 (ethyleneoxy).sub.19 ethanol (2) Liquid emulsion polymer 1 percent Brookfield Model LVT viscosity, pH 9, #2 spindle at 12 rpm, 25° C. (3) Evaluation in latex paint base Formulation 3A interior vinyl acrylic flat latex paint Formulation 3B interior acrylate semigloss latex paint LEP, wt lbs LEP thickener (100% solids basis)/100 gallons Viscosity 24 hr Stormer viscosity, KU LL Leneta Leveling 0-10 LAS Leneta AntiSag 0-12
TABLE II ______________________________________ COMPARISON OF THICKENERS Paint Thickener Haake Visc. Test Thickener 1% Visc. Base wt Visc. KU ______________________________________ 3D-1 LEP-2A 400 3A 4.5 3.65 101 3B 2.75 0.9 85 3D-2 LEP-2E 9200 3A 3.5 -- 110 3B 2.0 -- 106 3D-3 HEC 1100-1450 3A 5.0 -- 96 3B 3.25 -- 94 3D-4 HEMC 800-1050 3A 5.25 -- 88 3B 3.5 -- 91 3D-5 MC-J 1000-1500 3A 4.5 1.75 95 3B 2.5 1.3 80 ______________________________________ Notes*: LEP2A: 48.0 MAA/42.0 EA/10.0 VSE1A LEP2E: 47.8 MAA/42.0 EA/10.2 VSE1C HEC: Hydroxyethyl cellulose QP 15,000 (Union Carbide Corp) HEMC: Hydroxyethyl methylcellulose XD7603.03 (The Dow Chemical Co.) MCJ: Hydroxypropyl methylcellulose Methocel® J20MS (The Dow Chemcial Co.) Paint Base: Formulation 3A or 3B Thickener, wt: Lbs (100% solids)/100 gal Haake visc.: Viscosity (poise) at 10,000 sec.sup.-1 Visc. KU: 24 hr Stormer viscosity
TABLE III ______________________________________ LATEX PAINT PERFORMANCE Vinyl-Acrylic Acrylic Paint Type Flat Semigloss* Thickener LEP-2A MC-J LEP-2A MC-J ______________________________________ Loading (lbs/100 gal) 4.5 4.5 2.5 2.5 Stormer Visc. (24 hr KU) 101 95 84 80 Leneta Leveling 7/10 4/10 5/10 4/10 Leneta Anti-Sag 11/12 9/12 12/12 12/12 Gardner 60° Gloss -- -- 43 43 Scrub (cycles) 463.sup.1 658.sup.1 1075.sup.2 1081.sup.3 Color Acceptance.sup.4 OK OK OK Poor Stormer Visc. (4 wks, 120° F.; KU) 103-107 95 81 94-92 Paint pH 9.4 8.5 9.2 9.1 Spattering Minimal Exces- Minimal Exces- sive sive ______________________________________ Notes*: VinylAcrylic Interior Flat Latex Formulation 3A Acrylic Semigloss Latex Formulation 3B MCJ Methocel® J20MS (The Dow Chemical Company) .sup.1 Avg. of 4 tests .sup.2 Avg. of 2 tests .sup.3 One test .sup.4 Color acceptance: Borden Aquablak G; Tenneco Thalo Blue, Thalo Green and Medium Yellow Rubbed up.
TABLE IV ______________________________________ VISCOSITY, CPS AT 25° C., pH 9 Conc: Salt 0% 0.25% 0.50% 0.75% 1.00% ______________________________________NaCl 300 1090 1200 1125 850 Na.sub.2 SO.sub.4 300 780 910 920 905 MgCl.sub.2 300 >2500 470 Floc -- ______________________________________
TABLE V ______________________________________ BROOKFIELD VISCOSITY* Latex* Initial 2% LEP-2A ______________________________________ Everflex® E 10 cps 170cps Airflex® 500 7.5cps 600 cps Ucar® 366 10 cps 290 cps ______________________________________ *Everflex® E Vinylacrylic copolymer (55% solids; W. R. Grace & Co.)Airflex® 500 Vinyl acetateethylene latex (55% solids; Air Products & Chemicals) Ucar® 366 Vinyl acetateacrylic copolymer latex, sometimes called "vinylacrylic latex" (55% solids; Union Carbide Corp.) Brookfield Viscosity #2 Spindle, 12 rpm, 25° C., pH 9.0
Claims (30)
CH.sub.2 ═CYZ (II)
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